Uniformly dyed water-swellable cellulosic fibers

ABSTRACT

Uniformly dyed water-swellable cellulosic fibers obtained by dyeing cellulosic fibers, in the swollen state, with a dye of the formula &lt;IMAGE&gt;   where D is a radical of a diazo component of the aniline, aminoazobenzene, aminophthalimide, aminonaphthalimide, anthraquinone or benzanthrone series, R is alkyl of 1 to 4 carbon atoms or phenyl which is unsubstituted or substituted by chlorine, bromine, methyl, methoxy or ethoxy and R1 is phenyl which is unsubstituted or substituted by chlorine, bromine, methyl, ethyl, methoxy, ethoxy, benzyloxy, phenoxy, chlorophenoxy, unsubstituted or N-substituted carbamoyl or sulfamoyl, unsubstituted or N-substituted phthalimidyl, alkoxycarbonyl of 1 to 8 carbon atoms, cyano or phenylsulfonyl.

The invention relates to uniformly dyed water-swellable cellulosicfibers, said fibers being fast to washing, dry cleaning, sublimation andlight and being produced by contacting water-swellable cellulosic fiberssuccessively or simultaneously with water, ethylene glycol or aderivative of ethylene glycol and, while the fibers are still swollen,with an essentially water-insoluble dye of the formula ##STR2## where Dis a radical of a diazo component of the aniline, aminoazobenzene,aminophthalimide, aminonaphthalimide, anthraquinone or benzanthroneseries, R is alkyl of 1 to 4 carbon atoms or phenyl which isunsubstituted or substituted by chlorine, bromine, methyl, methoxy orethoxy and R¹ is phenyl which is unsubstituted or substituted bychlorine, bromine, methyl, ethyl, methoxy, ethoxy, benzyloxy, phenoxy,chlorophenoxy, unsubstituted or N-substituted carbamoyl or sulfamoyl,unsubstituted or N-substituted phthalimidyl, alkoxycarbonyl of 1 to 8carbon atoms, cyano or phenylsulfonyl.

The radicals D of the diazo componennt may be substituted; examples ofsuitable substituents are, in the aniline series, fluorine, chlorine,bromine, methyl, trifluoromethyl, ethyl, methoxy, ethoxy, phenoxy,nitro, cyano, methylsulfonyl, ethylsulfonyl, phenylsulfonyl,alkoxycarbonyl of 1 to 8 carbon atoms, acetylamino, benzoyl,unsubstituted or N-substituted carbamoyl or sulfamoyl, oxdiazolyl orphenyloxdiazolyl; in the aminoazobenzene series, chlorine, bromine,nitro, methyl, ethyl, methoxy or ethoxy; in the aminophthalimide andaminonaphthalimide series, chlorine, methyl, cyano and -- at the imidenitrogen -- alkyl of 1 to 8 carbon atoms, alkyl of 2 or 3 carbon atomssubstituted by alkoxy of 1 to 8 carbon atoms, phenoxyalkyl, phenylalkylor unsubstituted or substituted phenyl, the alkyl radicals beinguninterrupted or interrupted by oxygen; in the anthraquinone andbenzanthrone series, chlorine or bromine.

Examples of alkyl radicals R are butyl, propyl, ethyl and preferablymethyl.

Examples of N-substituted carbamoyl or sulfamoyl radicals, and ofalkoxycarbonyl radicals of 1 to 8 carbon atoms, which R¹ may representand the aniline radicals D may contain are: CONHCH₃, CONHC₂ H₅, CONHC₃H₇, CONHC₄ H₉, CONHC₆ H₁₃, ##STR3## CONH(CH₂)₃ OC₂ H₄ OC₂ H₄ OC₆ H₅,CONHC₂ H₄ OH, CONHC₃ H₇ OCH₃, CON(CH₃)₂, CON(C₂ H₅)₂, CON(C₄ H₉)₂,##STR4## the corresponding sulfamoyl groups, and COOCH₃, COOC₂ H₅, COOC₃H₇, COOC₄ H₉, COOC₆ H₁₃, ##STR5## COOC₂ H₄ OH, COOC₂ H₄ OCH₃, COOC₂ H₄OC₂ H₅ and COOC₂ H₄ OC₄ H₉.

Unsubstituted or N-substituted phthalimidyl radicals are radicals bondedin the 3-position or 4-position, which may be substituted, at thenitrogen, by, for example, alkyl of 1 to 8 carbon atoms, alkyl of 2 or 3carbon atoms substituted by alkoxy of 1 to 8 carbon atoms, phenylethylor phenoxyethoxypropyl.

In additon to those already mentioned, specific examples ofN-substituents are: CH₃, C₂ H₅, n- or i-C₃ H₇, n- or i-C₄ H₉, C₅ H₁₁, C₆H₁₃, C₈ H₁₇, ##STR6## (CH₂)₃ OCH₃ , (CH₂)₃ OC₂ H₅, (CH₂)₃ OC₃ H₇, (CH₂)₃OC₄ H₉, ##STR7## C₂ H₄ OCH₃, C₂ H₄ OC₂ H₅, C₂ H₄ OC₄ H₉, (CH₂)₃ OC₂ H₄OCH₃, (CH₂)₃ OC₂ H₄ OC₂ H₅ and (CH₂)₃ OC₂ H₄ OC₄ H₉.

Preferred carbamoyl, sulfamoyl and phthalimidyl radicals are thosesubstituents which contain phenyl groups, especially CONHC₂ H₄ C₆ H₅,CONHC₆ H₅, CONH(CH₂)₃ OC₂ H₄ OC₆ H₅, ##STR8## SO₂ NHC₂ H₄ C₆ H₅, SO₂NH(CH₂)₃ OC₂ H₄ OC₆ H₅ or ##STR9## where T is C₆ H₅, C₂ H₄ C₆ H₅, (CH₂)₃OC₂ H₄ OC₆ H₅ or ##STR10##

The invention relates in particular to fibers which have been dyed withdyes of the formula I in which D is phenyl substituted by fluorine,chlorine, bromine, methyl, trifluoromethyl, ethyl, methoxy, ethoxy,phenoxy, nitro, cyano, methylsulfonyl, ethylsulfonyl, phenylsulfonyl,alkoxycarbonyl of 1 to 8 carbon atoms, acetylamino, benzoyl, carbamoylor sulfamoyl which are N-substituted by alkyl of 1 to 8 carbon atoms, byphenyl or by phenyl which is substituted by chlorine, methyl or methoxy,oxdiazol-5-yl, 3-phenyloxdiazol-5-yl, 4-phenyloxdiazol-2-yl, phenylazo,phenylazo substituted by chlorine, bromine, nitro, methyl, ethyl,methoxy or ethoxy, CONH(CH₂)₃ OC₂ H₄ OT¹ or SO₂ NH(CH₂)₃ OC₂ H₄ OT¹ ;##STR11## where n is 0 or 1, T is C₆ H₅, C₂ H₄ C₆ H₅, (CH₂)₃ OC₂ H₄ OC₆H₅ or ##STR12## T¹ is alkyl of 1 to 8 carbon atoms, benzyl, phenylethyl,cyclohexyl, phenyl or tolyl, T² is methyl, chlorine or bromine, R isalkyl of 1 to 4 carbon atoms, phenyl or phenyl substituted by chlorine,bromine, methyl, methoxy or ethoxy, and R¹ is phenyl, or phenylsubstituted by chlorine, bromine, methyl, ethyl, methoxy, ethoxy,benzyloxy, phenoxy, chlorophenoxy, alkoxycarbonyl (where alkoxy is of 1to 8 carbon atoms), cyano, phenylsulfonyl, CONHT³ or SO₂ NHT³, or##STR13## where T³ is alkyl of 1 to 8 carbon atoms, cyclohexyl, benzyl,phenylethyl, phenyl, phenyl substituted by chlorine, methyl, methoxy orethoxy, or (CH₂)₃ OC₂ H₄ OT¹.

Specific examples of diazo components are: o-, m- or p-nitroaniline, o-,m- or p-cyanoaniline, 2,5-dichloroaniline, 2,4,5-trichloroaniline,2-chloro-4-nitroaniline, 2-bromo-4-nitroaniline, 2-cyano-4nitroaniline,1-amino-4-methyl-2-nitrobenzene, 1-amino-4-methoxy-2-nitrobenzene,1-amino-4-chloro- or -bromo-2-nitrobenzene,1-amino-2-methyl-4-nitrobenzene,1-amino-2-trifluoromethyl-4-chlorobenzene,1-amino-2methoxy-4-nitrobenzene, 2-amino-4-chlorobenzophenone,4-amino-acetophenone, 4-aminobenzophenone, 2-aminobenzophenone,2-amino-diphenylsulfone, 2-, 3- or 4-aminobenzoic acid methyl ester,ethyl ester, propyl ester, butyl ester, isobutyl ester, β-ethylhexylester, β-methoxyethyl ester, β-ethoxyethyl ester and methyldiglycolester, 4-nitroanthranilic acid methyl ester, isobutyl ester,methyldiglycol ester and β -methoxyethyl ester, aminoterephthalic aciddimethyl ester and diethyl ester, 4-aminobenzoic acid amide,methylamide, propylamide, n-butylamide, cyclohexylamide andmethoxpropylamide, 2-, 3- or 4-aminobenzoic acid dimethylamide,pyrrolidide and morpholide, 5-aminoisophthalic acid diamide anddimethoxypropylamide, 3- or 4-aminophthalimide, -β-hydroxyethylimide,-γ-hydroxypropylimide, -phenylimide and -tolylimide, 3-amino-6-nitrophthalic acid β-hydroxyethylimide, 2,4-dinitro-6-bromoaniline,2,5-dichloro-4-nitroaniline, 2-chloro-4-aminobenzonitrile,2-amino-4-chlorobenzonitrile, 4-amino-naphthalic cid1,8-methoxyethylimide and methoxypropylimide,1-amino-4-nitrobenzene-2-methylsulfone, 2,4-dinitroaniline,1-amino-2nitrobenzene-4-sulfonamide, 1-amino-2-nitrobenzene-4-sulfonicacid n-butylamide, 1-amino-2-nitrobenzene-4-sulfonic acidβ-methoxyethylamide, 1-aminoanthraquinone,1-amino-4-chloroanthraquinone, 4-aminonaphthalic acid butylimide,##STR14## 4-aminoazobenzene, 2',3-dimethyl-4-aminoazobenzene,3,2-dimethyl-4-aminoazobenzene, 2,5-dimethyl-4-aminoazobenzene,2-methyl-5-methoxy-4-aminoazobenzene, 2,5-dimethoxy-4-aminoazobenzene,4'-nitro-2,5-dimethoxy-4-aminoazobenzene, 4'-nitro-4-aminoazobenzene,4'-nitro-2-methyl-5-methoxy-4-aminoazobenzene and4'-chloro-2-methyl-4-aminoazobenzene.

Examples of preferred diazo components are α-aminoanthraquinone,4-aminoazobenzene, 2,2'-dimethyl-4-aminoazobenzene, ##STR15##o-nitroaniline, 4-chloro-o-nitroaniline and 4-methyl-o-nitroaniline.

To manufacture the dyes of the formula I, a diazo compound of an amineof the formula II

    d--nh.sub.2                                                ii

may be reacted with coupling components of the formula III

    rcoch.sub.2 conhr.sup.1                                    iii

by conventional methods. Some of the dyes of the formula I are alreadyknown. ##STR16## where D¹ is a radical of the aniline or anthraquinoneseries, X is hydrogen, chlorine, methyl, ethyl, methoxy, ethoxy,phenoxy, chlorophenoxy, methoxycarbonyl, ethoxycarbonyl orethoxyethoxycarbonyl, Y is hydrogen, chlorine, methyl, ethyl, methoxy orethoxy and Z is hydrogen, methyl, methoxy, N-substituted carbamoyl,sulfamoyl or 3- or 4-phthalimidyl, are particularly valuable for dyeingthe fibers according to the invention.

In particular, D¹ in these compounds is the radical of one of thepreferred diazo components listed above.

From the point of view of their structure, the dyes of the formula I canbe described as substantially insoluble disperse dyes which as a rulecannot be applied to, for example, cotton. However, U.S. Pat. No.3,706,525 discloses a process which permits such dyes to be printed ontocellulose and cellulosic textiles. The general sense of the data onprocess conditions, given in the said patent, also applies to dyeingwith the dyes of the formula I. In addition, U.S. patent applicationSer. No. 691,496 describes further processes by means of which thefibers of the invention may be obtained. Of these, printing processesare preferred. In addition to cellulosic fibers, mixtures of cellulosicfibers and synthetic fibers, in particular cotton and polyester, mayalso be dyed and printed.

The fibers of the invention which are obtained have excellent fastnessproperties, amongst which wet fastness and in some cases also lightfastness may be mentioned. For example, in the case of prints, nostaining of any white ground occurs on laundering.

For dyeing and printing purposes, the dyes of the formula I areadvantageously converted to dye formulations which in addition to theabove dyes contain dispersing agents, water retention agents and water,with or without other constituents conventionally used in dyeformulations, eg. disinfectants or foam suppressants. Examples ofsuitable dispersing agents are anionic compounds, ie. dispersing agentswhich are also conventionally used for other disperse dyes. Specificexamples are condensation products of phenol, formaldehyde and sodiumsulfite, sulfomethylation products as a general category, andligninsulfonates. Water retention agents are, in particular, glycols andglycol ethers, eg. ethylene glycol and ethylene diglycol.

In the Examples which follow, parts and percentages are by weight,unless stated otherwise.

EXAMPLE 1

A cotton fabric is printed, by rotary screen printing, with an ink whichcomprises 10 parts of the dye of the formula ##STR17## 100 parts ofpolyethylene oxide of molecular weight 300 and 790 parts of a 3%strength alginate thickener, and the print is dried at 100° C. It isthen treated for 1 minute with hot air at 200° C, rinsed cold, soaped atthe boil, again rinsed cold, and dried. A light-fast and wash-fastyellow print on a white ground is obtained.

EXAMPLE 2

A polyester/cotton union fabric (weight ratio 67:33) is printed with apaste comprising 20 parts of the dye of the formula ##STR18## 120 partsof the reaction product of polyethylene oxide of molecular weight 300with boric acid in the molar ratio of 3:1 and 860 parts of a 10%strength alginate thickener. The print is dried at 105° C and treatedwith live steam for 6 minutes at 180° C. It is then rinsed with coldwater, soaped at 80° C, rinsed cold and dried.

A light-fast and wash-fast greenish-yellow print on a white ground isobtained.

EXAMPLE 3

A cotton fabric is roller-printed with a print paste which comprises 15parts of the dye of the formula ##STR19## 110 parts of polyethyleneoxide of molecular weight 350, 30 parts of oleic acid diethanolamide and845 parts of a 10% strength alginate thickener. The print is dried at100° C and is then fixed by treating it with hot air for 1 minute at195° C. It is finished as described in Example 1 and a fast,greenish-yellow print on a white ground is obtained.

EXAMPLE 4

A polyester/cellulose union fabric (weight ratio 67:33) is printed on ascreen printing machine with an ink which comprises 30 parts of the dyeof the formula ##STR20## 100 parts of the reaction product ofpolyethylene oxide of molecular weight 300 with boric acid in the molarratio of 3:1, 30 parts of oleic acid diethanolamide and 840 parts of a3% strength alginate thickener, and the print is dried at 110° C. It isthen treated for 5 minutes with live steam at 185° C, and finished asdescribed in Example 2.

A fast reddish-yellow print on a white ground is obtained.

EXAMPLE 5

A cotton fabric is treated on a padder with a solution which contains 20parts of the dye of the formula ##STR21## 300 parts of a 3% strengthalginate thickener, 550 parts of water and 130 parts of polyethyleneoxide of molecular weight 300. the liquor pick-up is 80%. The fabric isdried at 100° C and then treated for 5 minutes with live steam at 190° Cto fix the dye. Thereafter it is rinsed cold and washed at 90° C in aliquor which contains 3 parts of the condensation product of along-chain alcohol with ethylene oxide per 997 parts of water.

A yellow dyeing results.

Instead of a cotton fabric, a polyester/cotton fabric (weight ratio67:33) can be padded with the above solution. A yellow dyeing isobtained, with both constituents exhibiting the same shade. Fixing withhot air for 2 minutes at 195° C may be substituted for the treatmentwith live steam.

EXAMPLE 6

A cotton fabric is treated on a padder with a solution of 150 parts ofpolyethylene oxide in 850 parts of water, so as to give a liquor pick-upof 80%, and the padded fabric is dried at 100° C. The fabric is thenprinted, by rotary screen printing, with an ink which comprises 30 partsof the dye of the formula ##STR22## and 970 parts of a 10% strengthalginate thickener. The print is dried at 105° C, treated for 7 minuteswith live steam at 185° C and then finished by rinsing and soaping asdescribed in Example 1. A fast yellow print on a white ground isobtained.

In the Examples which follow the dyes are used as described inExample 1. Dyeings in the stated hues are obtained.

Marketable formulations are obtained from the dyes referred to in theExamples by, for example, the following method:

30 parts of dye, 6 parts of dispersing agent, 10 parts of waterretention agent, 1 part of disinfectant and about 53 parts of water aremilled in a stirred ball mill until the particle size is about 0.5 μm. Adispersion having a good shelf life is thus obtained.

    __________________________________________________________________________     ##STR23##                                                                    Ex-                                                                           ample                                                                             D                     R.sup.1               Hue                           __________________________________________________________________________     7                                                                                 ##STR24##            C.sub.6 H.sub.5       yellow                         8  "                                                                                                    ##STR25##            greenish yellow                9  "                                                                                                    ##STR26##            yellow                        10                                                                                 ##STR27##                                                                                           ##STR28##            reddish yellow                11                                                                                 ##STR29##                                                                                           ##STR30##            reddish yellow                12                                                                                 ##STR31##                                                                                           ##STR32##            reddish yellow                13  "                                                                                                    ##STR33##            yellow                        14  "                                                                                                    ##STR34##            yellow                        15                                                                                 ##STR35##            C.sub.6 H.sub.5       yellow                        16  "                                                                                                    ##STR36##            yellow                        17  "                                                                                                    ##STR37##            yellow                        18  "                                                                                                    ##STR38##            yellow                        19                                                                                 ##STR39##                                                                                           ##STR40##            yellow                        20  "                                                                                                    ##STR41##            yellow                        21                                                                                 ##STR42##            C.sub.6 H.sub.5       greenish yellow               22  "                                                                                                    ##STR43##            greenish yellow               23  "                                                                                                    ##STR44##            greenish yellow               24  "                                                                                                    ##STR45##            greenish yellow               25  "                                                                                                    ##STR46##            yellow                        26  "                                                                                                    ##STR47##            yellow                        27  "                                                                                                    ##STR48##            yellow                        28  "                                                                                                    ##STR49##            yellow                        29  "                                                                                                    ##STR50##            yellow                        30  "                                                                                                    ##STR51##            yellow                        31  "                                                                                                    ##STR52##            yellow                        32  "                                                                                                    ##STR53##            yellow                        33  "                                                                                                    ##STR54##            yellow                        34  "                                                                                                    ##STR55##            yellow                        __________________________________________________________________________

    ______________________________________                                         ##STR56##                                                                    Ex-                                                                           ample A           B     R.sup.1        Hue                                    ______________________________________                                        35                                                                                   ##STR57##  H                                                                                    ##STR58##     yellow                                 36    "           "                                                                                    ##STR59##     yellow                                 37    "           "                                                                                    ##STR60##     yellow                                 38    "           "                                                                                    ##STR61##     yellow                                 39    "           "                                                                                    ##STR62##     yellow                                 40    "           "                                                                                    ##STR63##     yellow                                 41    "           "                                                                                    ##STR64##     yellow                                 42    "           "                                                                                    ##STR65##     yellow                                 43    "           "                                                                                    ##STR66##     yellow                                 44                                                                                   ##STR67##  "                                                                                    ##STR68##     yellow                                 45    "           "                                                                                    ##STR69##     yellow                                 46    "           "                                                                                    ##STR70##     yellow                                 47    C.sub.6 H.sub.5                                                                           Cl                                                                                   ##STR71##     yellow                                 48    C.sub.6 H.sub.5                                                                           Cl                                                                                   ##STR72##     yellow                                 49    "           "                                                                                    ##STR73##     yellow                                 50    "           "                                                                                    ##STR74##     yellow                                 51    "           "                                                                                    ##STR75##     yellow                                 52    "           "                                                                                    ##STR76##     yellow                                 53                                                                                   ##STR77##  Cl                                                                                   ##STR78##     yellow                                 54    "           "                                                                                    ##STR79##     yellow                                 55    "           "                                                                                    ##STR80##     yellow                                 56    "           "                                                                                    ##STR81##     yellow                                 57    "           "                                                                                    ##STR82##     yellow                                 58    "           "                                                                                    ##STR83##     yellow                                 59                                                                                   ##STR84##  H                                                                                    ##STR85##     yellow                                 60                                                                                   ##STR86##  H                                                                                    ##STR87##     yellow                                 61    "           "                                                                                    ##STR88##     yellow                                 62    "           "                                                                                    ##STR89##     yellow                                 63                                                                                   ##STR90##  "                                                                                    ##STR91##     yellow                                 64    "           Cl    "              yellow                                 65    "           "                                                                                    ##STR92##     yellow                                 ______________________________________                                    

    __________________________________________________________________________     ##STR93##                                                                    Ex-                                                                           ample                                                                             D                            R.sup.1               Hue                    __________________________________________________________________________    66                                                                                 ##STR94##                                                                                                  ##STR95##            yellow                 67  "                                                                                                           ##STR96##            yellow                 68  "                                                                                                           ##STR97##            yellow                 69  "                                                                                                           ##STR98##            yellow                 70  "                                                                                                           ##STR99##            yellow                 71                                                                                 ##STR100##                                                                                                 ##STR101##           reddish yellow         72  "                                                                                                           ##STR102##           reddish yellow         73  "                                                                                                           ##STR103##           reddish yellow         74                                                                                 ##STR104##                                                                                                 ##STR105##           reddish-yellow         75  "                            C.sub.6 H.sub.5       reddish yellow         76  "                                                                                                           ##STR106##           reddish yellow         77                                                                                 ##STR107##                  C.sub.6 H.sub.5       reddish yellow         78  "                                                                                                           ##STR108##           reddish yellow         79  "                                                                                                           ##STR109##           reddish yellow         80                                                                                 ##STR110##                                                                                                 ##STR111##           yellow                 81  "                                                                                                           ##STR112##           yellow                 82  "                                                                                                           ##STR113##           golden yellow          83                                                                                 ##STR114##                                                                                                 ##STR115##           greenish yellow        84  "                                                                                                           ##STR116##           yellow                 85  "                                                                                                           ##STR117##           yellow                 86                                                                                 ##STR118##                                                                                                 ##STR119##           golden yellow          87                                                                                 ##STR120##                                                                                                 ##STR121##           greenish yellow        88  "                                                                                                           ##STR122##           yellow                 89  "                                                                                                           ##STR123##           yellow                 90  "                                                                                                           ##STR124##           yellow                 91  "                                                                                                           ##STR125##           yellow                 92  "                                                                                                           ##STR126##           yellow                 93  "                                                                                                           ##STR127##           yellow                 94  "                                                                                                           ##STR128##           yellow                 95                                                                                 ##STR129##                                                                                                 ##STR130##           golden yellow          96  "                                                                                                           ##STR131##           yellow                 97  "                                                                                                           ##STR132##           yellow                 98                                                                                 ##STR133##                                                                                                 ##STR134##           yellow                 99  "                                                                                                           ##STR135##           yellow                 100 "                                                                                                           ##STR136##           yellow                 101 "                                                                                                           ##STR137##           yellow                 102                                                                                ##STR138##                                                                                                 ##STR139##           yellow                 103                                                                                ##STR140##                                                                                                 ##STR141##           orange                 104 "                            C.sub.6 H.sub.5       orange                 105 "                                                                                                           ##STR142##           orange                 106                                                                                ##STR143##                                                                                                 ##STR144##           reddish yellow         107 "                                                                                                           ##STR145##           reddish yellow         108 "                            C.sub.6 H.sub.5       reddish yellow         109                                                                                ##STR146##                                                                                                 ##STR147##           reddish yellow         110 "                                                                                                           ##STR148##           yellow                 111 "                                                                                                           ##STR149##           yellow                 112 "                                                                                                           ##STR150##           yellow                 113                                                                                ##STR151##                  C.sub.6 H.sub.5       reddish yellow         114 "                                                                                                           ##STR152##           reddish yellow         115                                                                                ##STR153##                                                                                                 ##STR154##           yellow                 116 "                                                                                                           ##STR155##           yellow                 117 "                                                                                                           ##STR156##           yellow                 118                                                                                ##STR157##                                                                                                 ##STR158##           yellow                 119 "                                                                                                           ##STR159##           yellow                 120 "                                                                                                           ##STR160##           yellow                 121                                                                                ##STR161##                  C.sub.6 H.sub.5       yellow                 122 "                                                                                                           ##STR162##           yellow                 123 "                                                                                                           ##STR163##           yellow                 124                                                                                ##STR164##                                                                                                 ##STR165##           yellow                 125 "                                                                                                           ##STR166##           yellow                 126 "                                                                                                           ##STR167##           yellow                 127                                                                                ##STR168##                                                                                                 ##STR169##           yellow                 128 "                                                                                                           ##STR170##           yellow                 129                                                                                ##STR171##                                                                                                 ##STR172##           yellow                 130 "                                                                                                           ##STR173##           yellow                 131 "                            C.sub.6 H.sub.5       yellow                 __________________________________________________________________________

We claim:
 1. Uniformly dyed water-swellable cellulosic fibers, saidfibers being fast to washing, dry cleaning, sublimation and light andbeing produced by contacting water-swellable cellulosic fiberssuccessively or simultaneously with water, ethylene glycol or aderivative of ethylene glycol and, while the fibers are still swollen,with an essentially water-insoluble dye of the formula ##STR174## inwhich D is phenyl substituted by fluorine, chlorine, bromine, methyl,trifluoromethyl, ethyl, methoxy, ethoxy, phenoxy, nitro, cyano,methylsulfonyl, ethylsulfonyl, phenylsulfonyl, alkoxycarbonyl or 1 to 8carbon atoms acetylamino, benzoyl, carbamoyl or sulfamoyl which areN-substituted by alkyl of 1 to 8 carbon atoms, by phenyl of by phenylwhich is substituted by chlorine, methyl or methoxy, oxdiazol-5-yl,3-phenyloxdiazol-5-yl, 4-phenyloxdiazol-2-yl, phenylazo, phenylazosubstituted by chlorine, bromine, nitro, methyl, ethyl, methoxy orethoxy, CONH(CH₂)₃ OC₂ H₄ OT¹ or SO₂ NH(CH₂)₃ OC₂ H₄ OT¹ ; ##STR175##where n is 0 or 1, T is C₆ H₅, C₂ H₄ C₆ H₅, (CH₂)₃ OC₂ H₄ OC₆ H₅ or##STR176## T¹ is alkyl of 1 to 8 carbon atoms, benzyl, phenylethyl,cyclohexyl, phenyl or tolyl, T² is methyl, chlorine or bromine, R isalkyl of 1 to 4 carbon atoms, phenyl or phenyl substituted by chlorine,bromine, methyl, methoxy or ethoxy, and R¹ is phenyl, or phenylsubstituted by chlorine, bromine, methyl, ethyl, methoxy, ethoxy,benzyloxy, phenoxy, chlorophenoxy, alkoxycarbonyl (where alkoxy is of 1to 8 carbon atoms), cyano, phenylsulfonyl, CONHT³ or SO₂ NHT³, or##STR177## where T³ is alkyl of 1 to 8 carbon atoms, cyclohexyl, benzyl,phenylethyl, phenyl, phenyl substituted by chlorine, methyl, methoxy orethoxy, or (CH₂)₃ OC₂ H₄ OT¹.
 2. The fibers as claimed in claim 1 whereR in the formula is methyl.
 3. The fibers as claimed in claim 1 where Dis phenyl substituted by chlorine, bromine, methyl, methoxy, nitro,phenylsulfonyl, methoxycarbonyl, benzoyl, CONHT³, SO₂ NHT³,oxdiazol-5-yl or phenyloxdiazol-5-yl; or ##STR178##
 4. The fibers asclaimed in claim 1 where R¹ is phenyl, phenyl substituted by chlorine,bromine, methyl, methoxy, ethoxy, phenoxy, cyano, phenylsulfonyl, CONHT³or SO₂ NHT³.
 5. The fibers as claimed in claim 1 where T¹ is phenyl ortolyl.
 6. The fibers as claimed in claim 1 where T³ is phenylethyl,phenyl, phenyl substituted by chlorine, methyl, methoxy or ethoxy; or(CH₂)₃ OC₂ H₄ OT¹.
 7. The fibers as claimed in claim 1 where the dye hasthe formula ##STR179## in which T⁴ is hydrogen, chlorine, bromine ornitro, T⁵ is hydrogen, chlorine, bromine or methyl and R and R¹ have themeanings given in claim
 1. 8. The fibers as claimed in claim 1 where thedye has the formula ##STR180##
 9. The fibers as claimed in claim 1 wherethe dye has the formula ##STR181##
 10. The fibers as claimed in claim 1where the dye has the formula ##STR182##
 11. The fibers as claimed inclaim 1, wherein the fibers are cotton fibers.
 12. The fibers as claimedin claim 1, admixed or blended with synthetic fibers.
 13. The fibers asclaimed in claim 12, the synthetic fibers being polyester fibers.